JP2009509949A - Pesticide formulation with risk of crystallization and process for its production - Google Patents

Abstract

  Disclosed are formulations containing a pesticide that has the risk of crystallization in water when the formulation containing the pesticide as an active ingredient is dissolved. The formulations of the present invention are characterized by a long half-life ("shelf stability"), a long crystallization time after the formulation is dissolved in water, improved hydration properties and excellent emulsion stability. To do.

Description

  The subject of the present invention is, as the title indicates, pesticide formulations which have the problem of crystallizing in water when the formulations containing them as active ingredients are diluted. The formulations proposed herein have the following characteristics: long half-life (“shelf stability”), long crystallization time after the formulation is diluted with water, improved water Compatibility and excellent stability of the resulting emulsion.

  Another subject of the present invention is a process for the preparation of such pesticide formulations.

  The present invention relates to the field of pesticide formulations and anti-crystallization mixtures.

  One aspect of the present invention is an emulsion (known in the art as “EC”) (which is similar to an emulsion in water (“EW”)), which makes it Stability of other types of formulations used in agriculture to combat concentrated suspensions “CS” and all kinds of parasites. This is an improvement over the prior art.

  For industrial applicability of formulations with active ingredients (ai) that have a strong tendency to crystallize in water (or whose crystals tend to grow), they were placed in containers. Maintain active ingredients (agricultural practitioners use active ingredients in their containers, dilute with water, and then apply in the field) to prevent crystallization over a long period (eg 2 years) is required. Furthermore, once mixed with water, the active ingredient should remain inside the formed oil droplets without crystallizing. Furthermore, if it is to be applied in a field or place to fight parasites (eg disease vectors or lakes containing bacteria, fungi, viruses, etc., then water for use), it will crystallize The active ingredient clogs the filter, pre-filter and nozzle of the spraying device, so that effective and homogeneous application of the active ingredient is not possible.

  Finally, the emulsion must meet the FAO requirement (which indicates that the formulation should remain stable after mixing with water). This indicates the stability of the emulsion in the sense that after the formulation is mixed with water, the emulsion should not exhibit an oil phase or cream / oil or cream separation. This stability is not only applied in the period immediately after the formulation is diluted with water, but especially when the product is to be applied to a large surface area, the farmer is already diluted with water. It also applies to the common case where the preparation has to be left for a long period of time, which can be several days (for example, when the weather has deteriorated after the preparation has been diluted).

In particular, pesticide formulations that have the risk of crystallizing when diluted with water due to their chemical structure and associated physicochemical properties can be improved, however, the product is The following phenomena can easily occur when emulsified or suspended:
(I) In the case of EC and EW, due to the transfer from the oil phase to the water phase and the low but recognizable water solubility (active ingredients in water from 10 mg / L to 400 mg / L), Precipitation when
(Ii) concentrated suspension formulations (CS), microcapsule type formulations and crystals of the active ingredient already present (or possibly present) in the formulation prior to dilution with water In the case of another formulation, a rapid increase in the size of the crystals.

  The most similar prior art is exemplified by the fungicide tebuconazole. It has all the properties of easily crystallizing in water and is the most difficult active ingredient to formulate the formulation for later dilution in water. Several formulations of this fungicide are encompassed by the present invention. Emulsions (EC) or emulsions in water (EW) that meet the standard that the oil must not separate in 2 hours after emulsification according to the international standard CIPAC MT 36.1 approved by the FAO are currently available in the European Union (EU) ) Must be mentioned in particular that it is not commercially available. This indicates the complexity of formulating tebuconazo and another product with a similar crystallization tendency.

  ES 2062597 (which corresponds to EP 453899 by Bayer AG) describes N, N-dimethylalkylamides as anti-crystallizing agents and solvents in triazole-based (a group of chemicals including tebuconazole) formulations. ing. This solvent / anti-crystallizing agent is used commercially in the product called Tebuconazole 250 EW (Folicur®) in the European Union. ISP Investments claimed long before 1987 (EP 311632) about the use of alkyllactams in pesticide formulations (especially fungicides). This patent includes the use of N-octylpyrrolidone in a concentrated emulsion. However, this patent was revoked: N-octyl pyrrolidone had not previously been described for agricultural use. Bayer AG, in its EP 391168, claimed the third in the patent literature for the use of N-octylpyrrolidone. This time, it was about triazimenol and / or tebuconazole having an anti-crystallization effect. However, this patent does not relate to emulsions to which the present invention relates, but to aqueous liquids (highly diluted aqueous mixtures of the fungicides) that are prepared by farmers in the field just before application. Is. In this patent, we describe the anti-crystallization action (not the dissolution action) of ethoxylated and / or propoxylated ethanolamides for use in the emulsion itself. This is a technical feature that makes a difference from the prior art and is shared in all claims. N, N-dimethylalkylamides, just like alkyllactams (particularly N-octylpyrrolidone), simply have the property of being excellent solvents for triazole fungicides (particularly tebuconazole). There is also the fact that tebuconazole formulations containing these compounds escape crystallization in the sense that the active ingredient (tebuconazole) is an anti-crystallization agent [later named It is only due to the fact that it is very well dissolved in the oil phase provided by, so that tebuconazole does not penetrate into the aqueous phase and does not crystallize there. . Since water prevents crystallization of sugar sucrose, in a sense it can be said that water is an “anti-crystallization agent” for sugar sucrose. However, to describe the properties of water, no chemist will use the term “anti-crystallizing agent” for sugars. They will simply and accurately state that water is a solvent for sugar. Since the claimed ethanolamides are not good solvents for the compounds that form the subject of the present invention, the term “anti-crystallizing agent” is used appropriately in this document. The specification and claims of EP 391168 do not discuss emulsions (in which we are discussing this), but by adding N-alkyllactams, the farmer can Discusses aqueous mixtures for use in spray tanks (the idea of adding N-octylpyrrolidone to an emulsion has not been previously patented by ISP Investments and has not been patented by earlier patents) ). In the present invention, the presence of N-octylpyrrolidone has the sole function of providing an oil phase that sufficiently dissolves the pesticide, and has the anti-crystallization action described by Bayer in EP391168. Are not related. Similarly, the present invention is quite relevant to patents describing phosphates with anti-crystallization properties, which are different from those mentioned herein. Not done. Another fundamental difference from EP391168 is that concentrates that are emulsifiable in water (which is not claimed per se) described in the examples of EP391168 inevitably use water. Thus, the emulsion according to the present invention can contain water but does not require the presence of water. Furthermore, in the present invention, the amount of active ingredient (eg tebuconazole) can even be twice the amount (25% wt / wt) disclosed in EP 391168 (12.5%). (The higher the concentration, the greater the risk of crystallization).

  ES 655197 (which corresponds to EP 655197 by Bayer AG) describes alkoxyalkyl phosphates, which include suggestions for their use as anti-crystallizing agents in triazole-based formulations. Yes.

  US 3342673 (Mobil Oil Corp.) disclosed the use of N, N-dimethylalkylamides for use in emulsions long before Bayer AG EP 453899. The only difference between that patent by Bayer AG and the Mobil Oil Corporation patent (which has already disappeared) is that they are used for carbamate systems but not for triazole systems, Based on the reference in US Pat. No. 3,342,673 (while EP 453899 describes the use of N, N-dimethylalkylamides in emulsions for triazole systems).

  The products disclosed in EP 453899 and EP 655197 have the disadvantage that they are hardly commercially available, they are expensive, and most of them do not guarantee the required emulsion stability. Have.

  The present inventors show the same anti-crystallization effect as disclosed in the above document or an anti-crystallization effect superior to that, and at the same time, have significant emulsion stability against EC and EW of tebuconazole. In addition, we have found specific mixtures that generally impart significant emulsion stability to pesticide formulations with active ingredients that have similar crystallization problems and aqueous solubility similarities. The resulting emulsion stability is better than any commercially available product based on international standard tests of CIPAC and FAO / WHO. In summary, these formulations are better because they combine excellent emulsification (stable emulsion without cream or oil separation) with prevention of crystal formation. This problem has not been solved so far by the most similar prior art. This is because the most similar prior art emulsions are inferior (oil or cream separates within a short period of time) or they show partial crystallization. This problem is apparent when examining commercial formulations of certain pesticides (eg, tebuconazole). This problem has been solved by the present inventors in the following form. The term “pesticide” as used in the present invention encompasses a single pesticide, its various isomeric forms and a mixture of several pesticides. Should be understood.

BRIEF DESCRIPTION OF THE DRAWINGS In order to assist in the description of the invention, the present specification includes a set of drawings. However, due to the nature of the invention and the content of the drawings, individual descriptions thereof are left behind after the embodiment described in the section entitled “Best Mode for Carrying Out the Invention”. It is best to leave. That is because doing so makes the understanding better and the interpretation more concise.

Preferred embodiments of the invention The present invention is based on the unprecedented properties of ethoxylated and / or propoxylated long chain alkylethanolamides. Such properties include that they dissolve and emulsify biocides that have a tendency to crystallize, and that they act as anti-crystallization agents for such biocides. It is. Although this type of compound has already been described in US Pat. No. 4,057,506 as useful for inclusion in powerful detergents, there is no mention of their use in agriculture, and of course, No mention is made of their anti-crystallization properties. In particular, ethoxylated and / or propoxylated alkyl monoethanolamides are commercially described as “cleaning agents” and are not known for their use in agriculture. They have never been described as crystallization inhibitors or solvents for EC or EW. An obvious extension of the present invention is their use in concentrated suspensions, suspensions of capsules and powders, in which the emulsification described above is used. Properties and anti-crystallization properties are used as well.

  These ethanolamides have the general formula (I):

［式中、
ｎは、４以上でかつ２４以下の整数であり；
Ｒ_１は、１から１６回反復しているエトキシ基、１から１６回反復しているプロポキシ基、又は、１から８回反復しているエトキシ−プロポキシ基（ここで、エトキシ／プロポキシ基は、規則正しく交互に配列されているか、又は、任意の順番に配列されている）である］で表される。

[Where:
n is an integer of 4 or more and 24 or less;
R ₁ is an ethoxy group that repeats 1 to 16 times, a propoxy group that repeats 1 to 16 times, or an ethoxy-propoxy group that repeats 1 to 8 times (wherein the ethoxy / propoxy group is It is regularly arranged alternately or arranged in an arbitrary order).

  The hydrocarbon chain can be straight or branched.

In view of the data provided in the present invention, the ethoxylated and / or propoxylated alcohol (monoethanol) group can be any short chain alcohol or dialcohol (eg, n-propanol, isopropanol, n-butanol). Etc.) is an obvious extension. Another obvious extension to the scope of the present invention is that the dissolution and emulsification effects are fully retained even if more than 16 ethoxy (EO) and / or propoxy (PO) groups are used. . However, if they exceed 16 moles, their dissolving action (the dissolving action of the ethoxy and / or propoxy groups on pesticides that tend to dissolve and then crystallize in water) becomes too great. This is not appropriate for the purposes of the present invention. Preferred amounts are from 2 to 8 moles of ethoxy and / or propoxy groups, but suitable lengths are within or outside these ranges for the pesticide or selected pesticide mixture. It can be ascertained by trial and error until a suitable number of moles for R ₁ providing a good emulsion is found.

  It is of course expected that ethoxylated alkyl ethanolamides promote the transfer of the active ingredient from the oil phase to the aqueous phase and thus promote crystallization. Due to the presence of ethoxy groups, ethoxylated alkyl ethanolamides greatly facilitate the transfer of active ingredients emulsified in O / W to the aqueous phase than the same ethanolamide that is not ethoxylated. This is well known to those skilled in the art, provided that they all dissolve the active ingredient. It is generally obvious that ethoxy groups or propoxy groups facilitate the dissolution of the active ingredient, thanks to the unbonded electron pair of the oxygen atom. However, the inventors have surprisingly found that these ethoxylated ethanolamines not only dissolve the active ingredient without incorporation into the aqueous phase, but also inhibit its crystallization (which is expected). And the last effect to be measured), and they have been found to ensure particularly advantageous emulsification and hydration effects.

  It is necessary to mention this difference compared to the prior art disclosed by EP 453899. First of all, probably the most suitable compound for dissolution and crystallization prevention (preferred embodiment using the selected amide type), and indeed it is used industrially in agrochemical formulations under the trade name Hallcomid (Registered trademark) 8-10, Agneque (registered trademark) KE 3308, Genegen (registered trademark) 4296, Rhodiasolv (registered trademark) ADMA 10 (EP453899) are N, N-dimethyldecanamide and N , N-dimethyloctaneamide (all of these compounds have one amide group and one alkyl chain (preferably an alkyl chain having 8 to 10 carbons)).

In the present invention, ethoxylated and / or propoxylated alkylethanolamides are used, which differ from the prior art disclosed by EP 453899 in the following ways:
(I) In order to exert an effective action, the alkyl chain has a longer length than that disclosed, ie preferably 16 to 20 carbon atoms (though those disclosed in EP 453899 2 times).
(Ii) Furthermore, EP453899 discloses N, N-dimethylalkylamides. In the present invention, there is no functional group having a nitrogen atom. Such functional groups lead to significant differences in chemical structure, polarity and some physicochemical properties between the two types of compounds.
(Iii) Furthermore, what will be described is a very important point regarding chemical and functional differentiation in comparison with EP453899, but in the present invention, alkylethanolamides are ethoxylated, Properties completely different from those described in EP 453899 are imparted to the alkylethanolamides. In EP453899, N, N-dimethyldecanamides do not show any emulsifying effect and are completely incorporated into the oil phase. However, the ethoxylated ethanolamides show an emulsifying effect. This is because the ethoxylated portion tends to be located in the aqueous phase, while the alkylethanolamide portion remains in the oil droplets. Surprisingly, the fact that ethanolamides are ethoxylated and / or propoxylated is the short time when the readily crystallized active ingredient is incorporated into the aqueous phase as expected by one skilled in the art. It does not mean that it crystallizes inside. It is even more surprising that the use of ethoxylated and / or propoxylated ethanolamide has a very advantageous effect on EC of the easily crystallized product (great improvement in emulsion stability). That is. Conventionally and in practice (for example, in the case of Folicur), emulsions of tebuconazole remain uncrystallized over a long period of time based on the separation of oil that occurs in only 2 to 6 hours (obviously A poor quality emulsion, so that a high proportion of the active ingredient is not found in homogeneously emulsifiable liquids). In contrast, the use of ethoxylated alkylethanolamides prevents crystallization and provides significant stability to the emulsion (oil and cream do not separate for longer than 2 days). ).

  In summary, by using ethoxylated ethanolamides (not to mention, ethoxylated ethanolamides are used in combination with other ingredients of the formulation. It is an acceptable emulsion when used alone. Or because it is impossible to achieve all of the essential effects required of a suspension, which means that virtually all co-formulants of any formulation This applies to unexpected and advantageous properties for use in formulations of active ingredients that readily crystallize in water.

  The problem is that ethoxylated and / or propoxylated ethanolamides by themselves cannot act as a single supplemental formulation. In order to solve this problem, it is necessary to find an additional solvent, preferably one that also has anti-crystallization properties and works in conjunction with alkylethanolamides. The inventors have determined that alkoxyalkyl phosphates, ie, phosphate esters having an ether group and an alkyl chain in the alkylol chain (these are chemical structures, physicochemical properties, and in particular, solubilization properties and The emulsification properties differ from the alkoxyalkyl phosphates described in EP 655197 (which do not have an ether bond), which have a significant solubilizing effect (solubility in water) Found that a special structure for the solvent for low biocides has been imparted). The use of alkoxyalkyl phosphates (in combination with ethoxylated ethanolamides) is also provided here for the first time for application as a solubilizer as well as an anti-crystallization agent.

  Such alkoxyalkyl phosphates have the general formula (II)

［式中、
Ｒ^１は、−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ又は−Ｈであり；
Ｒ^２は、−（ＣＨ_２）_ｘ−Ｏ−（ＣＨ_２）_ｙ又は−Ｈであり；
Ｒ^３は、−（ＣＨ_２）_ｕ−Ｏ−（ＣＨ_２）_ｖ又は−Ｈであり；
ｎ、ｘ及びｕは（互いに独立して）、１、２、３、４、５又は６であり；
ｍ、ｙ及びｖは（互いに独立して）、１、２、３、４、５、６、７、８、９又は１０であり：
Ｒ_１、Ｒ_２及びＲ_３は（互いに独立して）：
（ｉ）エーテル基を有する上記構造であるか、又は、
（ｉｉ）水素である］
で表される。

[Where:
R ¹ is — (CH ₂ ) _n —O— (CH ₂ ) _m or —H;
R ² is — (CH ₂ ) _x —O— (CH ₂ ) _y or —H;
R ³ is — (CH ₂ ) _u —O— (CH ₂ ) _v or —H;
n, x and u (independent of each other) are 1, 2, 3, 4, 5 or 6;
m, y and v (independent of each other) are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10:
R ₁ , R ₂ and R ₃ (independent of each other):
(I) the above structure having an ether group, or
(Ii) is hydrogen]
It is represented by

For example, if no radical is hydrogen, tris- (alkoxyalkyl) phosphate is obtained. When one radical is H, the compound is bis- (alkoxyalkyl) phosphate. We intend to point out that it is preferable to use tris- (alkoxyalkyl) phosphates (these compounds have ionic properties). The presence of more ether linkages within the R ₁ , R ₂ and R ₃ chains is an obvious extension of the compounds of formula (II), which have similar properties as emulsifiers. Tris- (2-butoxyethyl) phosphate was described in patent DE 523802 for quite different applications long before 1929. From that time to now, there is no disclosure of the use of (II) in the “Tris” form for use in agrochemical formulations of compounds that have a tendency to crystallize in water upon dilution (also self-explanatory) Absent).

  With respect to the use of alkoxyalkyl phosphates of the formula (II) according to the invention, it must be pointed out further differences from the use of phosphates according to EP 655197. In the above patents, phosphates are used by way of example together with anti-crystallization agents already disclosed by EP 453899, or alkylbenzene sulfonates (which are substances not used in the present invention). Used in combination.

  The problem is that the anti-crystallization activity by the already described compounds belonging to the present invention is maintained under extreme conditions of use, i.e. EC, EW and CS are kept at a natural temperature of less than -15 [deg.] C for a fairly long period of time. In some areas, or in those conditions where they are left in the tank of the spreader for a long time (eg 3 weeks) after dilution, in some cases not sufficiently effective. . This problem of providing further resistance to crystallization that has already been improved is unexpectedly associated with high molecular weight hydrophilic polymers that exhibit anti-crystallization properties (which are well known to the well-known polypropylene glycols and polyethylene glycols). Is different) in the EC and EW. The inventors have surprisingly found that inclusion of polymers conventionally used as anti-crystallizing agents in concentrated suspension formulations, in emulsions, in emulsions in water, and microemulsions. I realized that it was effective. These polymers are (but not excluded) natural or synthetic polymers such as polyvinyl pyrrolidone, mixed polymers of polyvinyl pyrrolidone and (meth) acrylates or polyvinyls, gum arabic, carboxymethyl cellulose, polyvinyl Such as alcohol and polyvinyl acetate, and derivatives and similar substances developed by certain companies. Its novelty lies in their new use in connection with EC and EW according to the present invention. As can be seen from FIGS. 12A and 12B, the inventors have found that they exert an anti-crystallization effect even before crystals are formed. For example, EP 655197 shows that this type of polymer can be used advantageously in sprayable liquids, but has well-known adhesive properties (in this patent, No mention is made of the crystallization effect). The use of this type of polymer in concentrated suspension formulations (CS) is also part of the prior art, however, CS already contains large sized crystals (which contain crystals of the active ingredient). Unlike EC and EW, which should not be included at all, there is a difference that the purpose of the polymer is to prevent the crystal dimensions from increasing excessively. In other words, the use of the above polymer is encompassed in the prior art, but as an inhibitor of crystal growth and not as an inhibitor to prevent crystal formation in the oil phase. Thus, the use of such polymers in agrochemical formulations (eg, wettable powders, granules that can be dispersed in water, and concentrated suspension formulations) where crystals are a partial component of Although known from the art, their use in EC to prevent crystallization does not belong to the prior art. The novelty of introducing the above high molecular weight polymer in the present invention is the film outside the oil droplet (this is shown in FIGS. 12A and 12B by the white halo around the oil droplet, The absence of hydrophilic polymers in the formulation, which are not present). This film prevents all crystallization even before the smallest crystals are formed. If for some reason crystals have already formed, they are prevented from “drawing” more active ingredients to grow towards the outside of the oil droplets (FIG. 12A) and the crystals agglomerate. I can't. This can be confirmed by micrographs of oil droplets in the emulsion according to the invention and can be understood by comparative tests carried out in the presence and absence of such polymers. It is also known from the prior art to use the above polymers in sprayer tanks independently of ES and EW. It is the farmer who introduces the polymer from separate packaging units from those containing EC or EW (this is not part of the invention).

  The inclusion of a hydrophilic polymer of the type described in the previous paragraph in the oil formulation was also novel and required extensive research. In particular, in the case of EC and EW that do not contain any water, it is not obvious how to incorporate the polymer into the oil phase so that the polymer dissolves in the oil phase. Many tests conducted by the inventors have shown that if the supplemental formulation is not properly selected, the polymer will not be solubilized and an unacceptable mass will be formed in EC or EW. Thus, the problem is how to incorporate high molecular weight polymers that inhibit crystal formation into the oily formulation (the EC can be emulsified with oil and active ingredients, and later prior to field application. It contains an emulsifier to make it possible, but in the case of EW or CS, water is already present before being diluted in the sprayer tank and it is easy to incorporate a hydrophilic polymer ( This is a difference from the prior art)). The inventors have solved this problem by using a mixing process that includes continuous steps and by using a novel mixture of supplemental formulation agents.

Furthermore, a clearly non-polar phase that forms oil droplets in which the active ingredient is dissolved and retained therein presents another problem to be solved in compounds with some degree of polarity. To do. Such compounds are not completely soluble in most of the typical solvents in EC and EW (eg, light or heavy naphtha) (eg, those named in paragraph 24). This problem is difficult to solve and can inter alia balance the polarity of the non-polar phase and the solubility of the active ingredient therein and the partial solubility of the active and non-polar phase in water. Desired. For this purpose, the inventors have conducted research and have identified certain compounds that are conventionally used in agrochemical formulations as suitable auxiliary formulating agents for the oil phase, such as (limited) without being) were selected as follows: N- octyl pyrrolidinone, N- decyl pyrrolidinone, the N- dodecyl pyrrolidinone (generally, has a C ₁ -C ₁₆ alkyl group N- alkylpyrrolidinones), gamma - butyrolactone, cyclohexanone, N- _(typically, N- alkyl caprolactams having C 4 _{-C 16} alkyl group) octyl caprolactam, acetic acid esters and generally esters of fatty acids having _C 4 _{-C 22} alkyl chain And citrates, lactates, phthalates and oxalates. The inventors preferably select N-alkylpyrrolidinones, naphtha and gamma-butyrolactone, but are not limited thereto.

The compounds listed in the previous paragraph as substances that can be used to form oil droplets have the disadvantage of some solubility in water (except for naphtha). This poses a risk regarding the crystallization of the active ingredient. This is because they can act as phase transfer catalysts (oil to water). For these reasons, in order to completely solve the problem of oily droplet formation, we have surprisingly found that alcohols (whether linear or branched) are surprising. In particular, it has been found that the active ingredient is effective in the formation of strong oil droplets from which it cannot escape. Unlike many alcohols described in the literature for use in EC, in particular, unlike the alcohols described in EP 655197 (ES2117748, page 11, lines 60 to 62), The alcohols selected in the invention are not short-chain alcohols (less than 5 carbon atoms). However, the present invention does not include the inclusion of alcohols. They are therefore merely present in the formulation. Because they are used industrially in the preparation (solubilization) of sodium alkylarylsulfonates or calcium alkylarylsulfonates (this belongs to the prior art). In particular, linear and branched alcohols (whether primary or tertiary), preferably having C ₅ -C ₁₂ chains, are selected as suitable compounds within the scope of the present invention. . The use of short chain alcohols (less than 5 carbon atoms) is not advantageous with respect to the strength of nonpolar droplets under the conditions of the present invention. Alcohols exceeding C ₁₂ is not a good solubilizer for compounds encompassed by the present invention.

  Furthermore, a suitable emulsifier must also be added to reduce the size of the droplets and prevent oil and cream separation. This prevention of separation (improving the emulsion) has already been largely ensured by using ethoxylated and / or propoxylated ethanolamides. However, the use of emulsifiers, preferably (but not exclusively), polysorbates, ethoxylated and / or propoxylated fatty alcohols, ethoxylated and / or propoxylated castor oil, ethoxylated and / or propoxy It is convenient to use an emulsifier selected from the group consisting of tristyrylphenols, and mixtures thereof, and other commercial products made for this purpose.

Overall, the present invention relates to various compounds (wherein each of the compounds has its own function and interaction, EC and EW (in this case the concentrate already contains water). Are) in the state of being applied diluted with water,
(I) a main solvent (5 to 50% wt / wt) for the active ingredient, for example (but not limited to), consisting of N-alkylpyrrolidones, N-alkylcaprolactams, naphtha and the like;
(Ii) a co-solvent (2 to 25% wt / wt) for the active ingredient in non-polar droplets, preferably consisting of medium chain (C ₅ -C ₁₂ ) alcohols;
(Iii) a co-solvent and anti-crystallizing agent (10 to 80% wt / wt) for the active ingredient in nonpolar droplets, consisting of an alkoxyalkyl phosphate, part of which is located in the aqueous phase;
(Iv) the active ingredient consisting of ethoxylated and / or propoxylated alkylethanolamides whose ethoxy and / or propoxy ends are located in the aqueous phase and whose hydrocarbon chains are located inside the oil droplets Emulsifiers, anti-crystallizing agents and co-solvents (5 to 80% wt / wt);
(V) a compound with a clear emulsifying action located in both the aqueous phase and the oil phase, where the compound belongs to the following group (but not limited to): polysorbates, ethoxylation And / or propoxylated fatty alcohols, ethoxylated and / or propoxylated castor oil, ethoxylated and / or propoxylated tristyrylphenols and mixtures thereof) (1 to 20% wt / wt);
(Vi) Water-soluble polymers of the following types (not limited): polyvinylpyrrolidone, mixed polymers of polyvinylpyrrolidone and (meth) acrylates or polyvinyls, gum arabic, carboxymethylcellulose, polyvinyl alcohol and polyvinyl acetate, As well as derivatives and similar compounds developed by certain companies, where the polymer is located in the aqueous phase around the water droplets, whereby the polymer is crystallized of the active ingredient in the aqueous phase In the case where it is already formed, and the polymer prevents, among other things, the active ingredient from leaking from the oil droplets into the aqueous phase) (0.1 to 10). % Wt / wt).

  We attempted to determine the applicable scope of these formulations and provide a specific list of pesticides. It is well known that different compounds with different chemical structures require specific proportions and specific types of solvents, emulsifiers and other auxiliary formulation agents with respect to EC and EW. . However, it is customary in the literature and patents to extend properties (such as anti-crystallization ability or solubility ability) from one compound to another having a similar chemical structure.

  This was done in both cases of EP655197 and EP453899. In the composition, the disclosed anti-crystallizing agents (N, N-dialkylamides) are described without mentioning all composition examples where it is appropriate to use N, N-dimethylalkylamides. Is intended for all types of triazoles having a bactericidal action. The inventors have found that some of the fungicides named in EP 655197 and EP 453899 have no crystallization problems at all. Propioconazole is one example. It has a chemical structure very similar to that of tebuconazole, but without crystallization problems in the emulsion (EC) when used in a conventional manner recommended by the emulsifier manufacturer, or in water There is no problem of crystallization in the emulsion (EW) (provided that the water content of the EW is less than 10%).

  The inventors have stated that the “risk” of crystallizing pesticides in EC or EW is not similar to the chemical structure, but rather specified to predict the risk of crystallization. It proved much more reasonable to evaluate the experimental parameters (or parameters calculated semi-empirically). In many studies, the inventors have found several types of pesticides that are at risk of crystallization and other pesticides that are not at risk of crystallization. Specifically, this risk is observed when 5 mL of EC or EW is diluted with 95 mL of water and kept in a refrigerator (1 ° C.), and then after 7 days, the emulsion is passed through a 5 μm filter. It shows what happens.

The experimental parameter is primarily the solubility in water or octanol, which is known as the octanol / water partition coefficient (K 2 _{O / W} or log P). The range of log P values for which the present invention is effective includes pesticides with a log P of 2.5 to 4.5. Another value that affects the tendency to crystallize is the Henry constant. This Henry's constant is related to the electric field inside the pesticide molecule and to the electric field around the oil droplet (molecule). Henry's constant is 0.0003 Pa. Pesticides that are less than m ³ / mol are the subject of the present invention. This discovery by the inventors is based on our own experience. Furthermore, the pesticides that are the subject of the present invention are solid at ambient temperature and more specifically have a boiling point above 40 ° C. Finally, this is very important, but the solubility of the pesticide in water must be taken into account. In the present invention, the water solubility range is 10 to 400 mg of pesticide per liter of water. This range means that if the solubility in water is very low, the pesticide has a very low tendency to crystallize away from the oil droplet, and if the solubility exceeds 400 mg / L, Solubility ensures that a small amount of pesticide placed in water is maintained in dissolved form and does not crystallize from the water if a good emulsifier system is selected. High enough. Because of these limitations, not only are preferred compositions according to the present invention arbitrarily selected, but instead of merely unduly extending the scope of the present invention by focusing solely on the structure of the molecules, The invention is selected such that it is meaningful.

These selection criteria for the present invention may include, among other things, the following pesticides (using internationally accepted names):
Atrazine, azinephos-methyl, bromazolone, bromconazole, butaphenacyl, chlorotolulone, coumatetralyl, cyclanilide, cyproconazole, 2,4-D, difenconazole, dimethomorph, diuron, ethoxysulfuron, fenamifos, fenhexa Mido, ferrimzone, flusilazole, fomesafen, fuberidazole, flaxilil, halofenozide, imazalyl, indanophan, iprovaricarb, isoproturon, linuron, MCPA, mefenpyr-diethyl, metconazole, methiocarb, nualimol, paclobutrazol, propanil, prothiodatron , Cimetrine, tebuconazole, triadimethone, triadimenol and tria Zamart. An advantageous property of the formulations discussed herein is that the oil droplets should contain only one compound or should contain more than one compound. This is not necessarily implied, and the subject matter of the present invention also includes mixtures of any of the above pesticides with another pesticide or synergist. In addition, it is possible to combine one of the above pesticides with another pesticide that is liquid at ambient temperature that helps to inhibit crystallization. When combined with the pesticide, which tends to remain in the oil droplets, even another pesticide that is solid at ambient temperature helps to inhibit the crystallization of the pesticide. The combination of pesticides is quite obvious as an extension of the present invention and is not subject to further discussion.

  Of course, the second subject can be formulated independently (thanks to the compounds and mixtures described herein) with or without crystallization problems. EC and EW formulations of pesticides. As described above, the first subject of the present invention is represented by readily crystallizing pesticides, but of any pesticide having a compound of the type described herein. Formulations are also included within what we desire to be the subject of the present invention. It is basically a suitable formulation in the EC and EW forms of pesticides. When the pesticide is not at risk of crystallization, the emulsifying and dissolving properties of ethoxylated and / or propoxylated alkylethanolamides and alkoxyalkyl phosphates together to reveal a good emulsion The combination of emulsifying and dissolving properties of such ethoxylated and / or propoxylated alkyl ethanolamides and alkoxyalkyl phosphates is clearly evident in the present invention (described first in the present invention). Is included in the range.

Preferred embodiment of the present invention (Example 1)
Example 1
A series of tebuconazole formulations (1000 g) having the following composition were prepared (percent is wt / wt):

  To ensure complete dissolution of the polyvinylpyrrolidone / methacrylate (PVDEM), a mixture was first prepared from the following ingredients (specified amounts): octyldecanamide 4 EO, isooctanol and N-octylpyrrolidone. . To it was then added PVDEM. A clear solution was obtained by moderate heating and stirring. This indicates that PVDEM—surprisingly—dissolved completely in a clearly non-polar phase. At the same time, another separate reactor was used to mix tebuconazole, Hostaphat B310, Soprophor 796 / P, Tween 20, and Emulsogen EL 400. After mixing it with an anchor stirrer, this second mixture was obtained in a clear form. Finally, the first mixture was mixed with the second mixture and then mixed using an anchor stirrer until a completely homogeneous mixture was obtained.

  The following tests were then performed: CIPAC MT 36.1 (emulsification and re-emulsification), CIPAC MT 39.1 (stability at low temperature), and CIPAC MT 46 (stability at high temperature).

  All formulations except formulation A6 (which showed some crystallization) and formulation A3 (which was insufficiently emulsified) were published in the official document “FAO Specifications for Plant Protection Products, Tebuconazole, AGP: CP / 369 "was found to meet the tolerances specified.

Example 2
In this example, the stability of the commercial product “Folicur® Tebuconazole 250 EW” is compared with that of the formulation described in Example 1, especially A1, [Soprophor® (instead of Emulsogen® EL 400). Trademark) 461 is added, isooctanol is reduced to 10%, Hostaphat® B310 is increased to 26%, Tween® 20 is replaced with Tween® 85, PVDEM is replaced with PVP-K15 (ISP) ), And the stability obtained by replacing with]. The formulation similar to that described in A1 was HPLC-MS (FIG. 3) (analysis conditions for the HPLC-MS: Agilent 1100 HPLC / SL ion trap, Hypersil ODS, mobile phase: acetonitrile, water and 0.1% Formic acid; AP-ESI detector), infrared analysis (FIG. 4), gas chromatography using a flame ionization detector (FIG. 5A), and gas chromatography using a mass spectrometer as a detector (FIG. 5B) Is characterized by This sample was designated Formulation B.

  The results of the emulsion stability test (CIPAC MT 36.1) are as follows.

  As is apparent from the above table, the emulsion stability of the Folicur® sample was inferior to that of Formulation B. This is because 1 mL of oil had already separated after 2 hours in a 100 mL graduated cylinder containing the formulation at a concentration of 5%. After 24 hours, the amount of oil separated was 3 mL. This period of 24 hours is typical under field conditions if the sprayer tank is left halfway because the process has to be interrupted due to bad weather or simply because the night is approaching. It is a typical one. Our formulation B showed excellent emulsion stability. It was found that the oily residue isolated in the Folicur® formulation consists primarily of N, N-dimethyldecanamide.

  A spray test was also performed at a pressure of 2 bar using a 250 μm nozzle and a 150 μm filter of the type normally used in the nozzles of the sprayer tank. Two sprayable liquids were prepared. One was based on Formulation B (0.25 liter in 100 liters of water) and the other was based on Folicur®. Both sprayable liquids were placed in 200 L drums and kept in a 2 ° C. refrigerator for 4 days. The spray test was then performed by recirculating 100 liters for 6 hours and spraying the liquid through a single nozzle. An additional drum that collects the sprayed liquid was also used to return the sprayed liquid back into the spray tank until the test was completed after 6 hours of running.

  The results in FIGS. 6 and 7 show that neither of the filters or nozzles clogged in either of the two sprayable liquids (Formulation B and Folicur®).

Example 5
Activity of Mixture of Alkoxyalkyl Phosphate and Ethoxylated / Propoxylated Alkylethanolamine In the EC composition described in Example 4, we used Hostaphat B310 (in the same amount) tri- (2-ethylhexyl phosphate). ) The ester was replaced with oleylethanolamide 4 EO with a mixture of equal parts decanoic acid dimethylamide and octanoic acid dimethylamide, which was designated Formulation C.

  The same spray test as in Example 4 was carried out for 6 hours at a pressure of 2 bar (100 liters containing 250 mL of emulsion “C”). As shown in FIG. 8, after 12 minutes of running, the nozzle filter and the nozzle itself were found to be clogged.

Example 6
Effect of replacement of oxyalkane phosphate with an alkyl ester according to the composition described in ES21178743 The test was carried out exactly as described in Example 5. In this case, Formulation B was partially modified by replacing Hostapat® B310 with tributyryl phosphate. Using both this new formulation E and formulation B, a spray test was performed as in Example 5 using a 150 μm metal filter. In the case of Formulation B, the filter was not soiled even after 6 hours, but the filter and nozzle used in the test using Formulation E were clogged as shown in FIG.

Example 7
Effect of replacement of ethoxylated alkylethanolamine with N, N-dimethyldecanamide according to the composition described in ES2062597 The test was carried out in exactly the same manner as described in Example 5. In this case, Formulation B was partially modified by replacing oleylethanolamide 4 EO with N, N-dimethyldecanamide. Using both this new formulation F and formulation B, a spray test was performed as in Example 5 using a 75 μm metal filter. In the case of Formulation B, the filter was not soiled even after 6 hours, but the filter and nozzle used in the test using Formulation E were clogged as shown in FIGS. It was.

Example 8
Influence on crystallization stability by addition of PVP-K90 (ISP)

In a test 100 mL measuring cylinder, 1 g of each preparation was emulsified with 99 mL of water. The resulting emulsion was maintained at 4 ° C. for 16 hours in the refrigerator. Finally, it was filtered and the separated crystals were weighed. The value for the reference formulation was 100, and the values for the remaining samples were expressed as a percentage of the R1 value.

  The addition of PVP-K90 clearly markedly improved the inhibition of crystal formation compared to the results obtained for A1 and A2.

  12A and 12B show two droplets with a white halo resulting from PVDEM. This is because when the droplets are very close to each other (see A), the fusion of the droplets is inhibited and / or the possibility of breakage is reduced, thus inhibiting crystallization. Is shown. In Photo B, taken a few seconds after Photo A, not only can you see that the marked small droplet is separated from another larger droplet, but also does not adhere or aggregate with the crystal. Can also be seen (wherein the crystals were added to this test to simultaneously check how the hydrophilic polymer protects the droplets from the formed crystals).

Example 9
Various types of pesticides (where all the pesticides have Henry's constants less than 0.0003 Pa.m ³ / mol, boiling points above 40 ° C., water solubility from 10 to 400 mg Inhibition of crystallization achieved by including a propoxylated alkylethanolamide in (/ L, log P value is from 2.5 to 4.5) using the pesticide described in paragraph 24 The following EW formulations were prepared: There was not enough capacity to carry out extensive testing with all the compounds described in paragraph 24, and also enough capacity to fine tune the amount of emulsifier for complete emulsification. Since there was no city, we limited the use of the following basic formulations in all cases (EO and PO indicate the number of moles of ethoxy and propoxy groups, respectively): ing).

  The table below shows the qualitative results obtained in two different tests. In the crystallization test, an emulsion consisting of 2% formulation in 98 mL water was maintained at 1 ° C. for 24 hours and then passed through a 25 μm metal filter. A minus sign indicates that no crystal is present, and a plus sign indicates that a crystal is present. The emulsion test shows the qualitative results obtained for the quality of the emulsion (phase separation). The worst emulsion (where the worst emulsion is still acceptable) is given a “+” and the good emulsion is given a “++”, the best The emulsions that are given are given “++++”. When evaluating the emulsion, the phase separation was observed and the time at which the phase separation occurred was measured. The triple plus sign (++++) means that no separation was observed at the end of 2 hours and complete re-emulsification was observed at the end of 24 hours. A single + sign means that some oil has separated after 2 hours.

  As is apparent from the above table, only ciduron and triazamate had crystallization problems. This indicates the “universality” of the mixture listed in paragraph 19 for inhibition of crystallization.

  At the same time, the emulsions were not perfect in all cases (in the sense of satisfying “FAO requirements”), but they were improved by slightly changing the ratio of emulsifiers to N-alkylpyrrolidinones. can do. In general, most of the emulsions are suitable for field application if used immediately after preparation. When using the same basic formulation, it is unlikely or impossible for a large group as discussed here to provide an EC with good properties with respect to the emulsion. . However, even with this basic formulation, in fact, in almost all cases, crystallization is inhibited and the emulsion is only subject to final adjustments based on trial and error involving an appropriate number of tests. (All of the above formulations can be improved to the point where they are well tolerated in up to about 25 tests).

Example 10
Effect of adding water to EC for the purpose of preparing an EW formulation. No problem. An aqueous emulsion formulation (EW) was prepared from the ingredients described in Example 2. However, in order to make room for 4% water, the amount of the ingredients was reduced by the same rate and the active ingredient was increased to 25.4%. This resulted in a difference between 25.4 and 20.6 in the isooctanol content in formulation B. The results for crystallization and emulsification in Example 2 were exactly the same in this case. From this, when the proportion of the component is reduced to add the desired amount of water starting from the EC, an improperly named “emulsions in water” (EW) (the formulation It can be concluded that (in case the water content in it is less than 10%) does not present any problem with regard to the advantageous effect of the formulation according to the invention.

Example 11
Stability at high temperature as tested by the “CIPAC MT 46” method The formulation described in Example 5 is placed in a heat-sealed 1 liter container made of polyterephthalate for 3 months in a refrigerator. Maintained at 1 ° C. After that period, the formulation was passed through a 0.1 μm filter under reduced pressure, indicating that the active ingredient was not crystallized.

  Reference is made to the accompanying drawings to assist in understanding what has been said above.

ここで、
Ｒ_１は、−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ又は−Ｈであり；
Ｒ_２は、−（ＣＨ_２）_ｘ−Ｏ−（ＣＨ_２）_ｙ又は−Ｈであり；
Ｒ_３は、−（ＣＨ_２）_ｕ−Ｏ−（ＣＨ_２）_ｖ又は−Ｈであり；
ｎ、ｘ及びｕは（互いに独立して）、１、２、３、４、５又は６であり；
ｍ、ｙ及びｖは（互いに独立して）、１、２、３、４、５、６、７、８、９又は１０である。
Ｒ_１、Ｒ_２及びＲ_３は（互いに独立して）：
（ｉ）エーテル基を有する上記構造であるか、又は、
（ｉｉ）水素である。
テブコナゾール、イソオクタノール、エトキシル化オクタデシルデカンアミド、リン酸２−ブトキシエチル、ポリオキシエチレンソルビタントリオレエート、エトキシル化／プロポキシル化トリスチリルフェノール及びポリビニルピロリドンを含んでいる本発明の好ましい実施形態のＦＴ−ＩＲスペクトルを示す図である。 テブコナゾール、イソオクタノール、エトキシル化オクタデシルデカンアミド、リン酸２−ブトキシエチル、ポリオキシエチレンソルビタントリオレエート、エトキシル化／プロポキシル化トリスチリルフェノール及びポリビニルピロリドンを含んでいる本発明の好ましい実施形態についてＨＰＬＣ−ＭＳで得られたクロマトグラフを示す図である。 テブコナゾール、イソオクタノール、エトキシル化オクタデシルデカンアミド、リン酸２−ブトキシエチル、ポリオキシエチレンソルビタントリオレエート、エトキシル化／プロポキシル化トリスチリルフェノール及びポリビニルピロリドンを含んでいる本発明の好ましい実施形態（フルオラネン（fluoranene）標準も一緒に含んでいる）についてＧＣ−ＦＩＤで得られたクロマトグラムを示す図である。ＭＤＭ−１２カラム、３０ｍ×０．２５μｍ×０．２５ｍｍ、流速：２ｍＬ／分、初期温度：５０℃、最終温度：２９０℃。 検出器として質量分析計を用いた以外は同じ分析条件下で得られたクロマトグラムを示す図である。 製剤Ｂを用いて噴霧試験を実施した後のフィルターを示す図である。 Ｆｏｌｉｃｕｒ（登録商標）製剤を用いて噴霧試験を実施した後のフィルターを示す図である。 製剤Ｃを用いて試験を実施した後のフィルター及びノズルを示す図である。 製剤Ｅ（右側）及び製剤Ｂ（左側）を用いて試験を実施した後のフィルターを示す図である。 製剤Ｆ（右側）及び製剤Ｂ（左側）を用いて試験を実施した後のフィルターを示す図である。 図９で示されているフィルター中に認められる凝集した結晶の顕微鏡写真を示す図である。 水相中に分散された油滴に対する親水性ポリマーの保護作用を例証する顕微鏡写真を示す図である。既に形成されている結晶に対する結晶化阻害効果も立証するために、結晶（矢印の先端の下にある大きな物体）が添加された。 水相中に分散された油滴に対する親水性ポリマーの保護作用を例証する顕微鏡写真を示す図である。既に形成されている結晶に対する結晶化阻害効果も立証するために、結晶（矢印の先端の下にある大きな物体）が添加された。 It is a figure which shows the compound represented by Formula (I). Where n is an integer greater than or equal to 4 and less than or equal to 24; R ₁ is an ethoxy group repeating 1 to 16 times, a propoxy group repeating 1 to 16 times, or repeating 1 to 8 times Ethoxy / propoxy groups (wherein the ethoxy / propoxy groups are regularly arranged alternately or in any order). The hydrocarbon chain can be linear or branched. It is a figure which shows the compound represented by Formula (II).

here,
R ₁ is — (CH ₂ ) _n —O— (CH ₂ ) _m or —H;
R ₂ is — (CH ₂ ) _x —O— (CH ₂ ) _y or —H;
R ₃ is — (CH ₂ ) _u —O— (CH ₂ ) _v or —H;
n, x and u (independent of each other) are 1, 2, 3, 4, 5 or 6;
m, y and v (independent of each other) are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
R ₁ , R ₂ and R ₃ (independent of each other):
(I) the above structure having an ether group, or
(Ii) Hydrogen.
FT- of a preferred embodiment of the invention comprising tebuconazole, isooctanol, ethoxylated octadecyldecanamide, 2-butoxyethyl phosphate, polyoxyethylene sorbitan trioleate, ethoxylated / propoxylated tristyrylphenol and polyvinylpyrrolidone It is a figure which shows IR spectrum. HPLC- for a preferred embodiment of the invention comprising tebuconazole, isooctanol, ethoxylated octadecyldecanamide, 2-butoxyethyl phosphate, polyoxyethylene sorbitan trioleate, ethoxylated / propoxylated tristyrylphenol and polyvinylpyrrolidone It is a figure which shows the chromatograph obtained by MS. Preferred embodiments of the invention comprising tebuconazole, isooctanol, ethoxylated octadecyldecanamide, 2-butoxyethyl phosphate, polyoxyethylene sorbitan trioleate, ethoxylated / propoxylated tristyrylphenol and polyvinylpyrrolidone (fluoranene ( Fig. 2 shows a chromatogram obtained with GC-FID for fluoranene (including standard). MDM-12 column, 30 m × 0.25 μm × 0.25 mm, flow rate: 2 mL / min, initial temperature: 50 ° C., final temperature: 290 ° C. It is a figure which shows the chromatogram obtained on the same analysis conditions except having used the mass spectrometer as a detector. It is a figure which shows the filter after implementing a spray test using the formulation B. FIG. It is a figure which shows the filter after implementing a spray test using Folicur (trademark) formulation. It is a figure which shows the filter and nozzle after implementing a test using the formulation C. FIG. It is a figure which shows the filter after implementing a test using the formulation E (right side) and the formulation B (left side). It is a figure which shows the filter after implementing a test using the formulation F (right side) and the formulation B (left side). FIG. 10 shows a photomicrograph of aggregated crystals found in the filter shown in FIG. 9. It is a figure which shows the microscope picture which illustrates the protective effect of the hydrophilic polymer with respect to the oil droplet disperse | distributed in the water phase. Crystals (large objects under the tip of the arrow) were added to also demonstrate the crystallization inhibitory effect on crystals that had already formed. It is a figure which shows the microscope picture which illustrates the protective effect of the hydrophilic polymer with respect to the oil droplet disperse | distributed in the water phase. Crystals (large objects under the tip of the arrow) were added to also demonstrate the crystallization inhibitory effect on crystals that had already formed.

Claims (11)

A pesticide formulation with a risk of crystallization, in the preparation of emulsion-type and emulsion-in-water formulations, diluted with water for application in the field and in dense form Both for the purpose of inhibiting crystallization of the active ingredient contained in the formulation together with a suitable auxiliary formulating agent and one or more active substances

[Where:
n is an integer of 4 or more and 24 or less;
R ₁ is an ethoxy group repeating from 1 to 16 times, a propoxy group repeating from 1 to 16 times, or an ethoxy / propoxy group repeating from 1 to 8 times (wherein the ethoxy / propoxy group is Regularly or alternately arranged, or arranged in any order); and
The hydrocarbon chain shown on the left side of the molecule can be straight or branched. ]
The pesticidal formulation essentially characterized by using ethoxylated and / or propoxylated alkyl monoethanolamide represented by The value of n is preferably 13 to 21 and more preferably 16 to 20, and ethoxy where R ₁ is preferably repeated 1 to 16 times and more preferably 2 to 8 times The pesticidal formulation with crystallization risk according to claim 1, characterized in that it is a group. Pesticide formulation at risk of crystallization, suitable for the preparation of emulsion type and emulsion type in water preparations for the purpose of inhibiting the crystallization of the active ingredient Together with one or more active substances (including the compounds described in claim 1)

[Where:
R ₁ is — (CH ₂ ) _n —O— (CH ₂ ) _m ;
R ₂ is — (CH ₂ ) _x —O— (CH ₂ ) _y ;
R ₃ is — (CH ₂ ) _u —O— (CH ₂ ) _v ;
n, x and u (independent of each other) are 1, 2, 3, 4, 5 or 6;
m, y and v (independent of each other) are 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
A pesticide preparation as described above, characterized in that it essentially comprises using a compound represented by:   The pesticidal formulation with risk of crystallization according to claim 3, characterized in that a phosphate ester of 2-butoxyethanol is preferably used. A pesticide composition comprising:
(I) a main solvent (selected from the group comprising N-alkylpyrrolidones, N-alkylcaprolactams, naphtha, cyclohexanone and gamma-butyrolactone) in an amount of 5 to 40% (wt / wt) for the active ingredient;
(Ii) 2 from 25% _(wt / wt) (chosen from alcohols linear or branched chain having C 5 _{-C 12} chain) the amount of co-solvent;
(Iii) a co-solvent and anti-crystallizing agent (selected from the group comprising a compound as claimed in claim 3) in an amount of 10 to 80% (wt / wt);
(Iv) 5 to 80% (wt / wt) emulsifier, anti-crystallizing agent and co-solvent (selected from the group comprising the compound of claim 1) for the active ingredient;
(V) Compounds having a clear emulsifying action in amounts of 1 to 20% (wt / wt) (polysorbates, ethoxylated and / or propoxylated fatty alcohols, ethoxylated and / or propoxylated castor oil, ethoxylated) And / or selected from the group comprising propoxylated tristyrylphenols and mixtures thereof);
(Vi) 0.1-10% (wt / wt) polyvinyl pyrrolidone, mixed polymers of polyvinyl pyrrolidone and (meth) acrylates or polyvinyls, gum arabic, carboxymethyl cellulose, polyvinyl alcohol and polyvinyl acetate, and Water-soluble polymers of the type, derivatives and copolymers thereof;
(Vii) optionally in an amount of 0.5 to 60% (wt / wt) water;
The said agrochemical composition characterized by including. A pesticidal formulation with a risk of crystallization by the compounds according to claims 1 and 3, characterized in that the formulation of the active pesticide ingredient used is:
(I) 2.5 to 4.5 logP
(Ii) 0.0003 Pa. Henry constant less than m ³ / mol (iii) Boiling point (iv) under atmospheric pressure above 40 ° C. Water solubility at 20 ° C. of 10 to 400 mg / L, said pesticidal formulation.   A pesticidal drug product having a risk of crystallization by the compound according to claims 1 and 3, wherein the compound used in the preparation of the pesticidal active ingredient is atrazine, azinephos-methyl, bromazolone, bromuconazole, butaphenacyl Chlorotolulone, coumatetralyl, cyclanilide, cyproconazole, 2,4-D, difenconazole, dimethomorph, diuron, ethoxysulfuron, fenamiphos, fenhexamide, ferrimzone, flusilazole, fomesafen, fuberidazole, flaxilil, halofenozide, imazalyl, Indanophan, iprovaricarb, isoproturon, linuron, MCPA, mefenpyr-diethyl, metconazole, methiocarb, nuarimol, paclobutrazol, propanil, prothioconazo , Pyridaphenthion, siduron, simetryn, tebuconazole, triadimefon, characterized in that it is selected from the group consisting of triadimenol and Toriazamato, the pesticidal agent formulation.   A pesticide preparation having a risk of crystallization containing polyvinylpyrrolidone and / or polyvinyl alcohol, wherein the polyvinylpyrrolidone and / or polyvinyl alcohol is used in combination with the compound according to claims 1 to 7. A pesticide preparation as described above.   An agrochemical formulation in the form of an emulsion, an infrared spectrum similar to the infrared spectrum shown in FIG. 3, the chromatogram shown in FIG. 4 (under the analytical conditions described in the specification, Obtained by HPLC / mass spectrometry), gas-chromatogram shown in FIG. 5A (obtained using a flame ionization detector), gas-chromatogram shown in FIG. 5B (detection) And obtained by using tebuconazole, isooctanol, ethoxylated octadecyldecanamide, 2-butoxyethyl phosphate, polyoxyethylene sorbitan trioleate, ethoxylated / The agrochemical formulation characterized by containing propoxylated tristyrylphenol and polyvinylpyrrolidone   A pesticidal formulation in the form of an emulsion in water according to claim 5, comprising tebuconazole, isooctanol, ethoxylated octadecyldecanamide, 2-butoxyethyl phosphate, polyoxyethylene sorbitan trioleate, ethoxylated / propoxylated The agrochemical formulation comprising tristyrylphenol, polyvinylpyrrolidone and water. A method of formulating EC and EW comprising the hydrophilic polymer of claim 5 (v), comprising:
(A) dissolving the polymer of claim 5 (v) with the compound of claim 5 (i), (ii), (iii) and (iv);
(B) dissolving the active ingredient using the compound according to claim 5 (v) and (iii);
(C) mixing (a) and (b) together;
(D) adding the hydrophilic polymer described in 5 (v) to the mixture (c);
(E) optionally adding water for an emulsion in water;
(F) homogenizing the final mixture;
(G) optionally filtering;
(Any of the above steps may optionally be heated).

Images